Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
  • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2190/00—Compositions for sealing or packing joints
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1376—Foam or porous material containing

Definitions

• the present invention relates to cellular materials, more particularly to soft and flexible materials made from expanded polyurethane polymer, especially those that can be used to make sealing, insulating or damping components.
• foamed seals that are intended for fitting onto types of doors, door trims, headlights, air conditioning units, etc.
• foamed polyurethane seals is carried out by depositing, by extrusion onto the part that has to be equipped with the seal, a material of suitable viscosity that develops into a foam by crosslinking in the open air or in a controlled atmosphere.
• the application of the material may be able to be carried out in a groove, on a former or on a smooth surface.
• Foam layers can also be manufactured, the material of suitable viscosity being deposited by extrusion as a sheet onto a medium such as paper or a glass fabric impregnated with silicone or with a fluorinated product, etc., or a plastic film, then, after adjustment of the sheet thickness and foaming and crosslinking of the product, the layer is peeled off then cut to the desired dimensions of the seals.
• the foam is laid on a non-nonstick substrate, such as a polyester film, that forms an integral part of the finished cellular product.
• the material to be deposited may be prepared in advance and be of a stable form that can be stored in an inert atmosphere until it is used. Such a system is said to be a “one-component” system. Or else the material to be deposited is formed from components stored separately from one another and mixed together in appropriate quantities just before application, using metering and mixing devices. This system is said to be a “two-component” system.
• one subject of the invention is firstly the use of at least one polyol (P) chosen from polyester and polyether polyols grafted by chains of at least one of the following: polystyrene, polyacrylonitrile and styrene/polyacrylonitrile copolymers and from polyester and polyether polyols in which at least one of the following: polystyrene, polyacrylonitrile and styrene/acrylonitrile copolymers is dispersed, as an incorporation into the formulation of the polyol constituent or of the polyol-polyamine constituent of a polyurethane forming the polymer matrix of a hydrolysis-resistant soft cellular material, said polyol or polyols (P) representing at least one part of said polyol constituent or at least one part of the polyol fraction of said polyol-polyamine constituent.
• P polyol
• styrene/acrylonitrile copolymer is understood to mean random copolymers, block copolymers and also combinations thereof.
• the polyols (P) according to the invention are especially polyether and polyester polyols, onto the backbone of which are grafted segments derived from at least one of the following: styrene and acrylonitrile.
• the backbones of the polyether and polyester polyols are for example a poly(ethylene oxide), a poly(propylene oxide) or a poly(propylene oxide-ethylene oxide).
• the backbone is: a copolymer incorporating ethylene oxide units and propylene oxide units, such copolymers possibly being block copolymers, in which an ethylene oxide oligomer is attached to a propylene oxide oligomer; random coploymers, where the ethylene oxide subunits and the propylene oxide subunits are randomly distributed; or polymers which are a combination of block polymers and random polymers.
• graft polyether polyols may be found in U.S. Pat. No. 4,670,477 in which they are described as modified polyether polyols.
• Graft polyols can be obtained commercially from several companies. Mention may be made of the polyols called “Polymer Polyol” by Bayer, those called “Graft Polyol” by BASF and those called “Co-polymer Polyol” by Dow.
• the polyol or polyols (P) advantageously represent at least 5% by weight, especially 10% by weight, of the polyol constituent or of the polyol-polyamine constituent of the polyurethane prepolymer.
• the cellular material may be in strip, sheet, strand or tube form for a seal, or part of a seal, for sealing, insulating or damping.
• composition intended for forming the polyurethane polymer matrix of a hydrolysis-resistant soft cellular material characterized in that it comprises:
• constituents (A) and (B) being especially chosen in such as way that said constituents (A) and (B) are able to react in an NCO/(OH+NH 2 ) molar ratio of at least 2, especially of about 2 to 5, preferentially 2 to 3.5.
• the polyol or polyols other than the polyols (P) and the polyamines capable of being incorporated into the formulation of constituent (A) may be chosen from the polyols and polyamines respectively having a backbone of the type: polyester; polycaprolactone; polyether; polyolefin, especially hydroxylated EVA copolymer; saturated or unsaturated polybutadiene; polyisoprene; and polydimethylsiloxane, for example: either of aliphatic and/or aromatic polyester type, preferably mostly aliphatic, especially derived from aliphatic glycols, possibly diethylene glycol, and from aliphatic and/or aromatic acids; or
• polyether type especially polyethylene oxide and/or polypropylene oxide or polytetrahydrofuran.
• the polyol or polyol-polyamine constituent is advantageously an oligomer with a molecular weight of around 10 000 g/mol or less, preferably of about 500 to 4 000 g/mol, and particularly from 1 500 to 3 500 g/mol.
• Its functionality is preferably about 2 as an upper value, and particularly from 1 500 to 3 500 g/mol.
• Constituent (B) may be chosen from simple molecules, in particular aromatic molecules, having at least two isocyanate functional groups, and also oligomers (of molecular weights which may especially be chosen from the abovementioned ranges), the above isocyanates modified in the form of prepolymers, and isocyanate prepolymers, these oligomers and prepolymers, of functionality at least equal to 2, having isocyanate end groups.
• the isocyante or isocyanates forming constituent (B) may thus be chosen from para-phenylene diisocyanate, trans-1,4-cyclohexane diisocyanate, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate, 1,5-naphthalene diisocyanate, methylenebis-(4-phenyl isocyanate) (pure MDI), crude MDI, toluene 2,4-diisocyanate (2,4-TDI), toluene 2,6-diisocyanate (2,6-TDI) and their mixtures, such as 80/20 TDI comprising 80% of the 2,4 isomer or 65/35 TDI, and also crude TDI (unpurified 80/20 TDI).
• the functionality is preferably about 2 as an upper value, particularly about 2 to 2.8.
• composition according to the invention may comprise, in addition, at least one conventional additive chosen from: particulate or pulverulent, organic or mineral fillers such as calcium carbonate and carbon black; plasticizers, colorants, stabilizers, surfactants, cell regulators and catalysts, said additive or additives usually being combined with constituent (A).
• particulate or pulverulent, organic or mineral fillers such as calcium carbonate and carbon black
• plasticizers, colorants, stabilizers, surfactants, cell regulators and catalysts said additive or additives usually being combined with constituent (A).
• filler is understood to mean here, in a general way, a product that is neither soluble in nor miscible with the polymer matrix, but is dispersible in the latter, making it possible to improve one or more properties or characteristics (mechanical properties, chemical properties, color, production cost) of the final compound.
• the composition is in the form of a viscous paste (one-component product) consisting of the polyurethane prepolymer having isocyanate end groups resulting from the reaction between constituents (A) and (B) with possible incorporation of at least one additive.
• the polyurethane prepolymer having isocyanate end groups may, according to one variant, have undergone a trialkoxysilylation reaction to yield a polyurethane prepolymer with trialkoxysilyl end groups.
• a trialkoxysilane capable of reacting with an NCO group may be a trialkoxyaminosilane, for example, an aminopropyltrialkoxysilane such as aminopropyltrimethoxysilane or even a trialkoxymercaptosilane.
• constituents (A) and (B) are intended to be mixed just before use (two-component system), in the presence of water as foaming agent, said mixture then being extruded at the time of application onto the part or support to give the cellular material.
• Yet another subject of the invention is a process for manufacturing a cellular material by extrusion of a composition as is defined above, characterized in that it comprises steps consisting:
• the pressurized gas may be preferably nitrogen, but also any other gas known for this purpose, namely air, carbon dioxide, n-pentane, etc.
• the crosslinking treatment in a humid atmosphere may be carried out under conditions known to those skilled in the art, for example in a temperature range from room temperature to 80° C. and in an atmosphere having a relative humidity of about 40 to 100%.
• the present invention also relates to a process for manufacturing a cellular material by extrusion of a composition such as is defined above, characterized in that it comprises steps consisting:
• the extrudable material may be deposited on a part that is intended to receive it, in particular, said material may be deposited as a band, or a strand or a ring in order to form a sealing, insulating or damping seal on said part.
• the extrudable material may also be deposited as a band, a layer or a disk on a support such as paper or a glass fabric impregnated with silicone, a fluorinated product, etc., or a plastic film, the support/extruded material assembly may possibly be passed between two rolls, to control the thickness of the extruded material, and then the foamed extruded material, possibly cut into the desired shapes and sizes for the sealing, insulating or dampening seal, may be detached.
• a support such as paper or a glass fabric impregnated with silicone, a fluorinated product, etc., or a plastic film
• extrusion is understood to mean here, in the broad sense, a technique in which a material in the fluid or viscous state is transported to an application orifice or nozzle. This term does not limit the invention to a technique for conforming the material, the latter being free to adopt, on exiting the orifice, dimensions substantially different from those of the nozzle outlet.
• the present invention also relates to a hydrolysis-resistant cellular material, obtained by extrusion of a polyurethane prepolymer having isocyanate end groups, foaming having been carried out by injection of pressurized gas and/or by chemical reaction between water and said isocyanate end groups, at least one polyol (P) is chosen from polyester and polyether polyols grafted by chains of at least one of the following: polystyrene, polyacrylonitrile and styrene/acrylonitrile copolymers and from polyester and polyether polyols in which at least one of the following: polystyrene, polyacrylonitrile and styrene/acrylonitrile copolymers is dispersed, being incorporated into the formulation of the polyol constituent or of the polyol-polyamine constituent of a polyurethane forming the polymer matrix of said cellular material, said polyol or polyols (P) representing at least one part of said polyol constituent or at least one
• the cellular material is advantageously in the form of a strip, a sheet, a strand or a tube for a sealing, insulating or damping seal.
• a polyurethane prepolymer was prepared by reacting a polyether grafted by a styrene/acrylonitrile copolymer with methylenebis(4-phenyl isocyanate) (MDI).
• MDI methylenebis(4-phenyl isocyanate
• This graft polyether is the one sold in the LUPRANOL range by BASF; it is characterized by an OH number of around 19.8 (expressed in mg of KOH per gram of product).
• the MDI used was a mixture of pure MDI having a functionality of 2 and a content of isocyanate NCO groups of 33.5% (in wt % of NCO equivalents per gram of product) and crude MDI having a functionality of 2.7 and a content of isocyanate NCO groups of 31.5% (in wt % of NCO equivalents per gram of product).
• the crude MDI represented 24% by weight of the total weight of isocyanates.
• an amine-type catalyst in an amount of 0.275% of the product, 0.4% of carbon black and 0.25% of a silicone surfactant were added. After homogenizing, the product was rapidly packaged under a dry atmosphere.
• the one-component product prepared above was extruded in the presence of pressurized nitrogen in a foaming machine of the type disclosed in EP-A-0 654 297, comprising:
• a mixer device fitted with a delivery tube for the viscous product and a delivery tube for the pressurized nitrogen;
• a delivery tube for the extrudable material equipped with a extrusion nozzle.
• the nitrogen dissolved in the one-component product.
• the material was exposed to atmospheric pressure, the reduction in pressure bringing about the release of nitrogen with the formation of gas bubbles that expanded the polymer.
• the extrusion conditions were adapted in order to form an extruded strand of around 6 mm in diameter.
• the nozzle was heated to 35° C. so as to keep the viscosity of the material at the desired value on exiting the extrusion channel.
• the extrusion operation was followed by a step of crosslinking the extruded strand in a humid atmosphere under two types of conditions: at room temperature and at a relative humidity of about 50 to 60%, or else in a hot atmosphere, for example at a temperature of 55° C. to 60° C., and at a relative humidity of 85% to 95% in a suitable chamber.
• the elongation of the cellular material as obtained was measured and then measured after hydrolysis (15 h in an autoclave at 120° C. in a moisture-saturated atmosphere under the conditions of the ISO 2440 standard).
• the elongation was measured on 6 mm diameter rods in accordance with the DIN 53571 standard, with a pull rate of 300 mm/minute and a 100 mm gap between the jaws.
• example 1 The method of example 1 was followed (same NCO/OH molar ratio) except that in place of the graft polyol, this same graft polyol was used as a blend with a polyether based on an ethylene oxide/propylene oxide mixture.
• the polyether based on an ethylene oxide/propylene oxide mixture was the one sold under the trademark LUPRANOL by BASF; it is characterized by an OH number of around 28 (expressed in mg of KOH per gram of product).
• polyol phase was composed only of polyether based on an ethylene oxide/propylene oxide mixture.
• Hydrolysis of a cellular material destroys the chains of the polyurethane matrix, which leads to an increase in the elongation of said material. In other words, the less a material is degraded, the smaller its variation in elongation.
• the table below shows, for each of the examples of the invention, the percentage variation in elongation normalized with respect to the variation in elongation obtained with the cellular material of the comparative example.
• This table also shows the height shrinkage or loss of height (in %) of the seal after the same aging.
• Example 2 Example 3
• Example 4 example Percentage ⁇ 1 ⁇ 2 15-25 40-60 100 variation in elongation Shrinkage ⁇ 5 ⁇ 5 ⁇ 5 16 >>20 (%)

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Sealing Material Composition (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (8)

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• 2005
  • 2005-08-17 FR FR0552529A patent/FR2889848B1/fr active Active
• 2006
  • 2006-08-03 JP JP2008526576A patent/JP2009504870A/ja not_active Withdrawn
  • 2006-08-03 KR KR1020087006376A patent/KR101351658B1/ko not_active IP Right Cessation
  • 2006-08-03 MX MX2008002131A patent/MX2008002131A/es active IP Right Grant
  • 2006-08-03 CN CN2013100332854A patent/CN103130975A/zh active Pending
  • 2006-08-03 CN CNA2006800297191A patent/CN101283013A/zh active Pending
  • 2006-08-03 US US12/063,823 patent/US20100260956A1/en not_active Abandoned
  • 2006-08-03 WO PCT/IB2006/052674 patent/WO2007020552A1/fr active Application Filing
  • 2006-08-03 BR BRPI0614313-0A patent/BRPI0614313A2/pt not_active IP Right Cessation
  • 2006-08-03 EP EP06780300A patent/EP1917284A1/fr not_active Withdrawn
• 2014
  • 2014-01-17 JP JP2014006728A patent/JP2014088577A/ja not_active Withdrawn
• 2016
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